Nothing beats test drive on your own and feel the difference. In fact, if you a car savvy person, you might test this more than what I am doing.
But I have test-driven both, and if you want, I can share with you my experience. Keep in mind though, response and power I cannot feel any difference.
1. I am a light-footed person when it comes to city driving, and thus I do not exceed 60-70km/h when I was testing it, nor the roads were bumpy enough. I can not feel any difference with the handling or the pickup or the suspension. Noise and whatsnot, I did not notice any difference.
2. One thing I do note is the feeling in the driver seat. I usually tend to have a low tilt on my steering wheel and a semi high seat as my driving setup. With Sienta, I got the feeling that I am driving a van (thus, the MPV class), while on BR-V the feeling was I am driving something sporty (the SUV/MPV crossover)
3. Another thing is the gearbox. Sienta have the Option to drop to "manual mode", thus make you change your own gear. While BR-V have the "S" gear, which I think will make you drop a gear and have more power. This is quite important, as I have to travel on Kulim-Gerik-Jeli road, and there are many lorries to overtake and a mountain to climb. I am more comfortable with BR-V one because I come from a Myvi, though I haven't got the chance to do this just yet (just got the car yesterday).
4. Tech-wise. Sienta > BR-V. This is apparent. For high-spec: Dual sliding doors, Optitron Meter with MID, DVR, Disc Brakes for both front and rear, cooler box, security tint included (though I do believe you want to do your own?). I would suggest if you go for Sienta, you upgrade to DVD-AVN. The reverse camera is much cooler in that version.
5. Interior-wise, BR-V highspec is leather while Sienta is fabric. One thing that needs to be commented is how much the Shotgun seat can be retracted to the back. BR-V can retract much more than Sienta, giving more legspace for my missus and the kid (yes, it's dangerous

) The feeling inside BR-V is also much roomier than Sienta. I did not test the third row seating though.
6. However, it needs to be said. Sienta's third row folds much more neatly than BR-V, as it stores under the 2nd row seat. For BR-V, the 3rd row is upright with a hook to secure it on the 2nd row seat. If you need the whole back space for cargo (2nd and 3rd row folded), Sienta also folds more neatly with 2nd row upright, 3rd row under 2nd row seat. For BR-V, I think you need to flatten 2nd and 3rd row.
Ultimately, I choose BR-V over Sienta because of Point (2) (sporty feeling vs van feeling), (3) (gearbox familiarity) and (5) (roomier, BR-V is bigger dimension-wise). But the rebate Toyota gave at that time (difference between BR-V and Sienta after rebate highspec is only 2-3k...) did made me torn up for a bit.
PS:- As you can see, it is more towards "how am I feeling driving this" rather than "how does the car feel/reacts/noise level" review.
How am I feeling driving this? I feeling noise from outside and not confident on thise lines at toll...hahah..